Vinyl resin



Patented May 1944 um'rap IKSTATE s PATENT orrica J v VINYL RESIN Ronald W. Staley, Pittsfleld, Mania, allignor to General Electric Company, a corporatlonoi New York No Drawing. Original application March 21, v 1942, Serial No.-435,636. Divided and thiaapplieation October 1, 1943, Serial No. 504,605

3 Claims. (erase-23) Broadly, my invention relates to the heat and light stabilization of resinous compositions produced by polymerizing compositions comprising a vinyl halide with or without otherbopolymerizable compounds. Among such compositions are: (1) the polyvinyl halides, such as for example polyvinylchloride, polyvinyl bromide; (2) vinyl resins produced by the conjoint polymerization of vinyl halides and vinyl esters of the lower alihatic acids, such as the copolymers of vinyl chloride with, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloracetate, vinyl chlorpropionate; (3) vinyl resins produced by the conjoint polymerization of vinyl halides and an acrylic compound, such as the copolymers of vinyl chloride with, for example, ethyl methacrylate, methyl methacrylate, methyl acrylate, methyl ethacrylate, benzyl acrylate, chlorbenzyl acrylate, methyl chloracrylate; and (4) many other vinyl resin copolymers, such as the copolymers of three component systems, for example,

vinyl chloride, vinyl acetate and ethyl methacrylate, etc. As will be understood by those skilled in the art, other multi-component copolymers may be used, the only requirement being that at least one of the components is a vinyl halide.

I have found that the class of compounds represented by the general formula:

R-lE-O are: undecylic, lauric, myrlstic, palmitic, oleic,

- linoleic, ricinoleic, stearic, nondecylic, etc. Illustrative examples of aryl radicals represented by Ar include: phenyl, tolyl, xylyl, naphthyl, chloro phenyl, chlorotolyl, etc. Where the radical has a substitute grouping the various isomers are included.

In the following examples, which aregivenby way of illustration bu't notby way of limitation, Example 1 shows the preparation of a typical stabilizer of my invention. The vinylite resin employed in the examples is a copolymer of vinyl chloride and vinyl acetate, the vinyl chloride being of the order of All parts are by weight. N

Example 1 l i v v Parts Phenyl stearate 30,85 Lead oxide (litharge) 19.15

Example 2 Vinylite'resin 99.5 Phenoxy lead stearate 0.5

The above components are milled'ior 3 minutes on differentialrolls; the front roll of which is heated with steam under a pressureoi .20 t 30 pounds per square inch. The compound after grinding is then molded for 5 minutes at a temperature of C. under a pressure of 2,000 pounds per square inch. Although these moldings conditions are more severe than those utilized normally in molding this type of resin-the resin darkens only slightly with little adherence to the mold. However, when the vinylite resin containing no stabilizer is sheeted. and molded as described above, the molded piece is considerably darker and in addition adheres to the mold to a very much greater extentthan the above sample containing the stabilizer. In fact, cutting the molding time to 1' minute for the unstabiliz'ed vinylite resin, which more nearly approaches normal molding conditions, -does not prevent the discoloration from being greater than that for the stalilized resin under the more severe molding conditions described above. .For

practical purposes, it can be said that 0.5% is the minimum amount of stabilizerthat should be used Example 3 Pan's Vinylite resin 99 Penoxy lead stearate 1 were sheeted and molded in the same way as described in ExampleZ. The piece did not darken or-adhere' to the :mold proving that it was stabil .-=Naphthoxyleadllinoleate 1 xyloxy lead montanate I. .Toloxy lead hypogeate ized towards this severe heat treatment.

Example 4 Parts Vinylite resin 98 i-Bhenoxy lead stearate 2 were treated as described under Example 2. Again a wellstabilizedmolded piece was obtained. More severe heat treatment causes ,.a faint In the compounding of plastic compositions foivarious uses, there may be included any of the common solvents, plasticizers, pigments, and

\ other modifying materials without detrimental opalescence but no discoloration to appear.

When 1% titanium dioxide was included in the formulation and the ,molded piece subjected to a carbonarc for 17 hours, "no discolorationcould bedetected showing that the piece was stabilized aaainstactinic radiation.

Excellent heat stabilizedcompositions were also obtained with the following compositions when treated and tested according to the conditions .ofExample 2.

.Ezample 5 I Parts Polyvinyl chloride .83 i-Plasticizer (methylpentachlorostearate).. ,fPhenoxy lead stearate 2 Example 6 Parts Poly-vinyl chloride 82 Plasticizer (#1488 Pyranol-a chlorinated ldiphenyl composition) l5 'Phenoxylead stearate 3 Example 7 Parts Copolymer of vinyl chloride (98%) and chlo- I 'robenzyl acrylate (2%) 98 'Phenoxy lead stearate 2 It is apparent from the examples-illustrating .the invention that small amounts of the phenoxy lead stearate exert a stabilizing effect on the vinyl in a quantity of at least'0.5% .stabilization is ef- 'fected. Amounts in excess of 5% may be used. "However, for economical reasons I prefer not. to

larger amounts.

It will be understood, of course, by those skilled in the .art that my .invention is not limited, to the-stabilization of polymers'or copolymers of a vinyl halide with phenoxy lead stearate. Instead of using phenoxy lead stearate I may use other 'aryloxy lead salts of monocarboxylic aliphatic acids having more than ten carbon atoms'in the acid radical, exam les of which are:

Phenoxy lead undecylate Phenoxy lead laurate Toloxy lead myristate (cresyl lead myristate) Toloxy lead stearate Toloxy lead oleate P henoxy lead oleate .Phenoxy lead ricinoleate .Xyloxy lead stearate jxyloxy lead palmitate Chlorophenoxy leadundecylate ,Chlorotoloxylead oleate Naphthoxy lead palmitate ,Phenoxy lead carnaubate The above compounds may readily be prepared by the method disclosed in Example 1 by using the corresponding tohrl, xylyl or naphthyl esters of the appropriate aliphatic monocarboxylic acid in place .of the phenyl stearate.

eifect upon the heat and light stability aflorded by these new stabilizers.

Various means well known to the art may be used forincorporating the stabilizers of this invention into the resinouscompositions. For example, the resin and plasticizer may be dissolved in a mutual solvent and intimately mixed followed by the evaporation of the solvent if the composition is not to be used as a varnish.

Sheeting on differential rolls, as was used in the examples, may also be used. It is important to obtain as intimate and complete dispersion or solution .of the stabilizer in the resin as is possible.

The stabilizers used in the present invention are to bedistinguished from the organo metallic salts such as, for example, diphenyl lead stearate, tributyl lead oleate, etc., in which the lead is joined directlyto the carbon atom of the organogroup and which generally are extremely poisonous and diiiicult and somewhat dangerous to handle. In marked contrast, the aryloxy lead salts of this invention are no more poisonous than the litharge and phenol from which they are made. The lead is joined to the aryl radical through an oxygen atom which, according to many tests which I have conducted, apparxresins. Thus, provided the stabilizer is present ently gives the compounds increased solubility in the vinyl halide polymers and copolymers. In fact, these new stabilizershave a greater solubllity in vinyl resins than any stabilizer that I have tested.- This isextremely important when it is desired to stabilize a. clear, unfilled resin.

The aryloxy lead salts also differ from the lead phenates which are the lead salts of phenols and which are easily hydrolyzable and of very limited solubility in vinyl halide resins.

The stabilized vinyl halide polymers and copolymers of this invention may be used not only for compression and injection molding compounds-but also for the preparation of varnishes, adhesives, castings, laminated products, etc.

Although in the above examples I have shown copolymers of, a vinyl halide containing in the order of 85% to 98% vinyl halide, I may use other copolymers in which the vinyl halide is present in lower concentrations, for example However, for maximum strength and flame resisting properties I prefer that the polyvinyl halide be present in the copolymers in an amount equal to at least 60%.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition comprising (1) the product of conjoint polymerization of a mixture comprising vinyl chloride and an acrylic ester, and (2) a heat and light stabilizer comprising a compound having the general formula:

wherein Ar is an aryl radical and R is an all phatic radical having at least 9 carbon atoms.

2. A composition as in claim 1 wherein the acrylic ester is chlorobenzyl acrylate.

3. A composition comprising (1) a copolymer obtained by conjoint polymerization of a mixture comprisingvinyl chloride and chlorobenzyl acrylate, and (2) phenoxy lead stearate.

RONALD W. STALEY. 

